Epoxy-containing polysiloxane oligomer compositions, process for making same and uses thereof

ABSTRACT

The present invention relates to stable, zero or low VOC epoxy-containing polysiloxane oligomer compositions that provide for a high degree of chemical resistance to compositions containing organic resins, while at the same time, maintaining or improving the flexibility of these organic resin-containing compositions, to processes for preparing epoxy-containing polysiloxane oligomer compositions, and to uses in coatings, sealants, adhesives, and composites containing the same.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. application Ser. No.13/329,430 filed Dec. 19, 2011, to which priority is claimed.

FIELD OF THE INVENTION

The present invention relates to epoxy-containing polysiloxane oligomercompositions, process of preparation, and uses thereof.

BACKGROUND OF THE INVENTION

The use of monomeric epoxy-functional silanes in coating, adhesive,sealant and composite applications is known. Recently, oligomericepoxy-functional silanes were disclosed as an important component ofwaterborne coatings. For example, U.S. Pat. Nos. 7,732,552 and 7,893,183disclose water-based coating compositions containing oligomericepoxy-functional silanes and one or more optional ingredients such assurfactants, pH adjusting agents, co-solvents, monomeric silanes,binders, crosslinkers and pigment paste dispersions. These oligomericepoxy-functional silanes are prepared from glycidoxy silane and/orcycloaliphatic epoxy silane having 2 or 3 alkoxy groups and less than1.5 equivalents of water in the presence of a catalyst, wherein thewater is continuously fed during the reaction.

Oligomeric epoxy-functional silanes can also be prepared by othermethods. For example, U.S. Patent Application Publication No.2010/0191001 discloses oligomeric epoxy-functional silanes prepared byusing 0.001 to less than 5 mol of water per mole of alkoxy function ofsilanes and not using any further hydrolysis or condensation catalystapart from boric acid as a hydrolysis catalyst and condensationcomponent.

Unfortunately, although the use of oligomeric epoxy-functional silanesin the coating compositions may improve the chemical resistance of thecoatings, the flexibility of the coatings may be compromised due to thehigher degree of cross-linking associated with the use of high molecularweight oligomeric epoxy-functional silanes. Further, the volatileorganic compound (VOCs) emissions in the form of alcohols from coatingscontaining the low molecular weight epoxy-functional silane oligomersdisclosed in the prior art may be high due to partial hydrolysis of themonomeric epoxy-functional alkoxysilane.

Accordingly, there is a continuing need in the coatings industry for astable, zero or low VOC containing epoxy-containing polysiloxaneoligomer composition that improves the chemical resistance of thecoatings while at the same time, maintains or improves the flexibilityof the coating containing this epoxy-containing polysiloxane oligomercomposition. The present invention provides an answer to that need.

SUMMARY OF THE INVENTION

In one aspect, the present invention is directed to an epoxy-containingpolysiloxane oligomer composition comprising:

(i) from 5 to 65 mole percent of a polysiloxane of the Formula (I):

(ii) from 10 to 55 mole percent of a polysiloxane of the Formula (II):

(iii) from 5 to 45 mole percent of a polysiloxane of the Formula (III):

(iv) from 1 to 20 mole percent of a polysiloxane of the Formula (IV):

and

(v) from 0.1 to 20 mole percent of a polysiloxane of the Formula (V):

wherein each occurrence of R¹ is —CH₂CH₂CH₂— and the mole percent ofcomponents (i), (ii), (iii), (iv) and (v) are based upon the sum of themolar amounts of components (i), (ii), (iii), (iv) and (v).

In another embodiment, the epoxy-containing composition of the presentinvention further comprises a stabilizing agent.

The epoxy-containing polysiloxane oligomer composition of the inventioncan be prepared by a process comprising:

(a) hydrolyzing a silane of the general Formula (VI):

wherein:

R¹ is —CH₂CH₂CH₂—;

R² is a monovalent alkyl group of from 1 to 3 carbon atoms; and

R³ is a monovalent alkyl group of from 1 to 3 carbon atoms;

in the presence of 2 to 15 moles of water per mole of the silane and,optionally, a hydrolysis catalyst, at a temperature of from 10° to 100°C. to provide an intermediate containing a silanol and an alcohol;

(b) removing the alcohol by distillation;

(c) removing water to condense the silanol to provide anepoxy-containing polysiloxane oligomer composition comprising from 5 to65 mole percent of the polysiloxane of the Formula (I), from 10 to 55mole percent of the polysiloxane of the Formula (II), from 5 to 45 molepercent of the polysiloxane of the Formula (III), from 1 to 20 molepercent of the polysiloxane of the Formula (IV), and from 0.1 to 20 molepercent of polysiloxane of Formula (V), wherein the Formulae (I), (II),(III), (IV) and (V) are as defined above, wherein the mole percents ofcomponents (i), (ii), (iii), (iv) and (v) are based upon the sum of themolar amounts of components (i), (ii), (iii), (iv) and (v); andoptionally

(d) adding a stabilizing agent.

In another aspect, the present invention relates to a compositioncomprising:

(i) the epoxy-containing polysiloxane oligomer composition as describedabove;

(ii) an organic resin containing at least one functional group selectedfrom the group consisting of epoxy, carboxylic acid, carboxylate anion,amino, ureido, urethane, mercapto, hydroxyl, alkoxysilyl andisocyaynato; and

(iii) at least one additional component selected from the groupconsisting of a solvent, surfactant, particulate metal, pigment,biocide, filler, thixotrope, catalyst, curing agent, pH adjusting agentand leveling agent.

These and other aspects will become apparent upon reading the followingdescription of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the effect of using a stabilizing agent to improvethe stability of the epoxy-containing polysiloxane oligomer composition.

FIG. 2 illustrates 60 degree gloss as a function of MEK double rubsafter three day post cure at room temperature for Example 6 andComparative Example D.

FIG. 3 illustrates 60 degree gloss as a function of MEK double rubsafter a ten-day post cure at room temperature for Example 6 andComparative Examples D and E.

DETAILED DESCRIPTION OF THE INVENTION

It has been surprisingly found that the epoxy-containing polysiloxaneoligomer composition of the invention provides a high degree of chemicalresistance to coatings, and at the same time, maintains or improves theflexibility of the coatings. In addition, the epoxy-containingpolysiloxane oligomer compositions of the invention impart very low orzero VOCs in the form of alcohols to the coating formulations.

Advantageously, in one embodiment, the epoxy-containing polysiloxaneoligomer composition of the invention comprises:

(i) from 5 to 65 mole percent, more specifically from 9 to 30 molepercent, and even more specifically from 10 to 20 mole percent of apolysiloxane of the Formula (I):

(ii) from 10 to 55 mole percent, more specifically from 30 to 50 molepercent, and even more specifically from 35 to 48 mole percent of apolysiloxane of the Formula (II):

(iii) from 5 to 45 mole percent, more specifically from 20 to 40 molepercent, and even more specifically from 25 to 35 mole percent of apolysiloxane of the Formula (III):

(iv) from 1 to 20 mole percent, more specifically from 5 to 18 molepercent and even more specifically from 7 to 15 mole percent of apolysiloxane of the Formula (IV):

(v) from 0.1 to 20 mole percent, more specifically from 2 to 8 molepercent, and even more specifically from 3 to 6 mole percent of apolysiloxane of the Formula (V):

wherein R¹ is —CH₂CH₂CH₂— and the mole percent of components (i), (ii),(iii), (iv) and (v) are based upon the sum of the molar amounts ofcomponents (i), (ii), (iii), (iv) and (v).

In another embodiment, the composition of the epoxy-containingpolysiloxane oligomer composition comprises from 5 to 65 peak areapercent, more specifically from 9 to 30 peak area percent, and even morespecifically from 10 to 20 peak area percent of component (i); from 10to 55 peak area percent, more specifically from 30 to 50 peak areapercent, and even more specifically from 35 to 48 peak area percent ofthe component (ii); from 5 to 45 peak area percent, more specificallyfrom 20 to 40 peak area percent, and even more specifically from 25 to35 peak area percent of component (iii); from 1 to 20 peak area percent,more specifically from 5 to 18 peak area percent and even morespecifically from 7 to 15 peak area percent of component (iv); and from0.1 to 20 peak area percent, more specifically from 2 to 8 peak areapercent, and even more specifically from 3 to 6 peak percent ofcomponent (v),

wherein the peak area percent of components (i), (ii), (iii), (iv) and(v) are based upon the sum of the peak areas as determined by the liquidchromatographic-mass spectrometric method (LC-MS Method) of components(i), (ii), (iii), (iv) and (v), as described herein.

In still another embodiment, the epoxy-containing composition has aviscosity of from 50 centistokes to 250 centistokes and morespecifically from 100 centistokes to 200 centistokes at 20° C. using abubble viscometer and carried out in accordance with ASTM method D-1545.

In another embodiment, the epoxy content is from 5.2 milliequivalentsper gram to 5.7 milliequivalents per gram and more specifically, from5.3 milliequivalents per gram to 5.6 milliequivalents per gram, asdetermined by a titration method involving the reaction of theepoxy-containing polysiloxane oligomer composition withhexadecyltrimethylammonium bromide in acetic acid and titrating theacetate anion with perchloric acid.

In yet another embodiment, the amount of releasable alcohol generatedfrom the reaction of the epoxy-containing polysiloxane oligomercompositions with water is less than 1 weight percent, more specificallyless than 0.5 weight percent, and even more specifically, less than 0.2weight percent, based upon the sum of the weights of components (i),(ii), (iii), (iv) and (v). In one embodiment, the weight percentreleasable alcohol is calculated using an 13-C NMR method in which therelative molar amount of the alkoxysilyl carbon SiOC is used tocalculate the weight of alcohol by multiplying the relative molar amountof the alkoxysilyl carbon SiOC by the molecular weight of the alcohol,and the molar amount of the methylsilyl carbon SiCH₃ is used tocalculate the sum of the weights of components (i), (ii), (iii), (iv)and (v) by multiplying the relative molar amounts of the methylsilylcarbon SiCH₃ by 162, and the weight percent releasable alcohol iscalculated by dividing the weight of alcohol by the weight of components(i), (ii), (iii), (iv) and (v) and multiplying the quotient by 100%.

In still yet another embodiment, the epoxy-containing composition of theinvention comprises less than 10 mole percent, more specifically, lessthan 5 mole percent, and even more specifically, less than 3 molepercent, of epoxy-containing polysiloxane oligomer components having 6or more silicon atoms, based upon the sum of the molar amounts ofcomponents (i), (ii), (iii), (iv) and (v). In yet still anotherembodiment, the number average molecular weight of the epoxy-containingpolysiloxane oligomer composition is between 500 grams per mole and 700grams per mole, as determined by a GPC method using polystyrenestandards, as described herein.

The epoxy-containing polysiloxane oligomer composition of the inventioncan be prepared by a process including the step of hydrolyzing a silaneof Formula (VI):

to form a silanol, removing byproduct alcohols, and condensing thesilanol by removing water,

wherein:

R¹ is —CH₂CH₂CH₂—;

R² is a monovalent alkyl group of from 1 to 3 carbon atoms; and

R³ is a monovalent alkyl group of from 1 to 3 carbon atoms.

Advantageously, R² and R³ are independently a methyl or ethyl group.

Specifically, the process of the invention comprises the steps of:

(a) hydrolyzing a silane of the general Formula (VI) in the presence of2 to 15 moles of water per mole of the silane and, optionally, ahydrolysis catalyst, at a temperature of from 10° to 100° C. to providean intermediate containing a silanol and an alcohol;

(b) removing the alcohol by distillation;

(c) removing water to condense the silanol to the desired polysiloxaneoligomer composition comprising from 5 to 65 mole percent, morespecifically from 9 to 30 mole percent, and even more specifically from10 to 20 mole percent of the polysiloxane of the Formula (I), from 10 to55 mole percent, more specifically from 30 to 50 mole percent, and evenmore specifically from 35 to 48 mole percent of the polysiloxane of theFormula (II), from 5 to 45 mole percent, more specifically from 20 to 40mole percent, and even more specifically from 25 to 35 mole percent ofthe polysiloxane of the Formula (II), from 1 to 20 mole percent, morespecifically from 5 to 18 mole percent and even more specifically from 7to 15 mole percent of the polysiloxane of the Formula (IV), and from 0.1to 20 mole percent, more specifically from 2 to 8 mole percent, and evenmore specifically from 3 to 6 mole percent of the polysiloxane of theFormula (V), wherein the Formulae (I), (II), (III), (IV) and (V) are asdefined above, wherein the mole percents of components (i), (ii), (iii),(iv) and (v) are based upon the sum of the molar amounts of components(i), (ii), (iii), (iv) and (v); and optionally

(d) adding a stabilizing agent, thereby making the polysiloxane oligomercomposition of the invention.

In the mixing step (a), the silane of Formula (VI) is hydrolyzed in thepresence of 2 to 15 moles of water per mole of the silane, specifically4 to 10 mole of water per moles of the silane, more specifically 5 to 7moles of water per mole of the silane, and optionally in the presence ofa catalyst.

The catalyst can be metal salts, alkyl ammonium salts, ion exchangeresins, carboxylic acids, mineral acids or metal chelates. Preferably,the catalysts are poor nucleophiles that do not readily react with theglycidoxy group of the silane and are poor catalysts for thecondensation of the silanol intermediate of step (a). These preferredcatalysts include carboxylic acids having a pK_(a) value of from 2 to 5,and more preferably from 3.5 to 4.8. Representative and non-limitingexamples of the catalysts include formic acid, acetic acid, propanoicacid, 1-butanoic acid, and tartaric acid. The acid catalyst can be usedat amounts ranging from 1 part per million (ppm) to 1 weight percentbased upon the weight of the silane of Formula VI, more specificallyfrom 5 ppm to 1.000 ppm and even more specifically from 50 ppm to 500ppm.

The hydrolysis temperature of step (a) is from 10° C. to 100° C., morespecifically, from 15° C. to 50° C., and even more specifically from 20°C. to 35° C. The hydrolysis of step (a) may be conducted under subatmospheric, atmospheric or super atmospheric pressure. The hydrolysispressure of step (a) is from 0.01 kilopascal to 200 kilopascal, and morespecifically from 80 kilopascal to 110 kilopascal. The hydrolysis timemay vary from 1 minute to 200 hours, more specifically from 1 hour to100 hours and even more specifically from 16 hours to 96 hours.

The alcohol byproducts can be removed by distillation. In oneembodiment, the removal of the alcohol from step (b) is carried out bydistillation at a pressure of from 0.01 kilopascal to 200 kilopascal,more specifically from 0.1 kilopascal to 110 kilopascal, and even morespecifically from 2 kilopascal to 105 kilopascal. The temperature forthe distillation can range from 10° C. to 100° C., more specificallyfrom 20° C. to 80° C., and even more specifically, from 25° C. to 60° C.

The removal of the water and condensation of the silanol of step (c) canbe accomplished by distillation. In one embodiment, the removal of thewater and condensation of the silanol of step (c) is carried out bydistillation at a pressure of from 0.01 kilopascal to 200 kilopascal,more specifically from 0.1 kilopascal to 110 kilopascal, and even morespecifically from 2 kilopascal to 105 kilopascal. The temperature forthe distillation can range from 10° C. to 100° C., more specificallyfrom 20° C. to 80° C., and even more specifically, from 40° C. to 75° C.The time to achieve the condensation can vary depending upon thetemperature and pressure used. Typically, the removal of water andcondensation of the silanol of step (c) requires from 1 hour to 200hours, more specifically from 2 hours to 24 hours and even morespecifically from 3 hours to 16 hours. The removal of the water andcondensation of the silanols can be assisted by sparging the reactionmixture of step (c) with an inert gas, such as for example nitrogen.

In one embodiment, the amount of water to be removed in step (c) can becalculated from the equation:W _(wd)=18.02M _(sa)[M _(wa) −M _(wr)−0.235x]

wherein:

W_(wd)=amount of water removed in step (c) in grams;

M_(wa)=number of moles of water added in step (a) per mole of silane;

M_(sa)=number of moles of silane added in step (a);

M_(wr)=number of moles of water reacted per mole of silanes:

x=1 if byproduct alcohol is ethanol, and x=0 if byproduct alcohol ismethanol, propanol or isopropanol.

The value of M_(wr) is from 1.25 moles water per mole silane to 1.45moles water per mole silane.

When the alcohol removed in step (b) forms an azeotrope with water, suchas in the case of ethanol, then for each mole of silane initially addedin step (a), 0.235 moles of water is removed in step (c) due to thewater:ethanol azetrope. The water:ethanol azeotrope is 4.4 weightpercent water and 95.6 weight percent ethanol, or 0.117 moles water permole ethanol. If the alcohol does not form an azeotrope with water, thenthe value of 0.235(x) is zero.

In one embodiment, the process is carried out in which in step (a) thesilane is 3-glycidoxypropylmethyldimethoxysilane or3-glycidoxypropylmethyldiethoxysilane and the amount of water is 5 to 7mole per mole of silane; the hydrolysis is carried out at a temperatureof from 20° C. to 30° C., a pressure of from 80 to 105 kilopascal, and atime ranging from 10 to 100 hours; removal of the alcohol of step (b) ata temperature of from 25° C. to 60° C., pressure of 2 to 105 kilopascalfor 1 to 10 hours; removal of the water and condensation of the silanolof step (c) at a temperature of from 40° C. to 75° C., pressure of from1 kilopascal to 15 kilopascal for a time of from 2 to 16 hours andwherein the amount of water removed per mole of silane is 62.1 gramswater per mole silane to 104.5 grams water per mole silane.

Optionally, a stabilizing agent can be added in a step (d) to theepoxy-containing polysiloxane oligomer composition after water isremoved. Suitable stabilizing agents are represented by Formula (VII):R⁴(OR⁵)_(p)  (VII)

wherein:

R⁴ is a boron atom, a HP(═O)(—)₂ group, a P(═O)(—)₃ group, a R⁶C(═O)(—)group, a polyvalent hydrocarbon group containing from 3 to 20 carbonatoms or a polyvalent heterocarbon group containing from 3 to 20 carbonatoms;

each R⁵ is independently a hydrogen, a R⁶C(═O)(—) group, or ahydrocarbon containing from 1 to 6 carbon atoms;

each R⁶ is independently a monovalent hydrocarbon group containing from1 to 5 carbon atoms;

p is an integer of from 1 to 6. Specifically, R⁴ is a boron atom or adivalent hydrocarbon group selected from the group consisting ofalkylene, cycloalkylene, alkenylene, arylene and aralkylene containingfrom 4 to 12 carbon atoms. More specifically, R⁴ is boron atom,P(═O)(—)₃ group, CH₃C(═O)(—) group, 2-methylpropylene,1-methoxy-2,3-propylene, 1,2-hexylene, or 2,3-dimethyl-2,3-butylene; R⁵is hydrogen, CH₃C(═O)(—), methyl or ethyl; and p is 1, 2 or 3.

Representative, non-limiting examples of the stabilizing agent are boricacid, phosphoric acid, phosphorus acid, acetic acid, acetic acidanhydride, glycerol, 2-methyl-1,3-propanediol,1-methoxy-2,3-propanediol, 1,2-hexanediol, and2,3-dimethyl-2,3-butanediol.

The stabilization agent can be used at amounts ranging from 100 partsper million to 25 weight percent, based upon the sum of the weights ofcomponents (i), (ii), (iii), (iv), and (v). Specifically, thestabilizing agent can be used at 100 parts per million to 2 weightpercent, based upon the sum of the weights of components (i), (ii),(iii), (iv), and (v), when R⁴ is boron atom, HP(═O)(—)₂, P(═O)(—), or(CH₃)C(═O)(—), or from 1 to 25 weight percent, based upon the sum of theweights of components (i), (ii), (iii), (iv), and (v), when R⁴ is apolyvalent hydrocarbon containing from 3 to 20 carbon atoms.

In one embodiment, the weight percents of components (i), (ii), (iii),(iv) and (v) are determined using a liquid chromatographic-massspectrometric (LC-MS) method, which was adapted from the ESI IonizationMethod disclosed in the reference, “Quantitative mass spectrometry oftechnical polymers: a comparison of several ionization methods”, W. Yan,et al., Eur. Mass Spectrom. 4, 467-474 (1998). The method involvesdissolving in acetonitrile the sample of the epoxy-containingpolysiloxane at a concentration of 0.1 weight percent before analysis.The analysis is carried out with a Waters LCT Premier XE LC/MSinstrument. An Atlantis dC18 (2.1×30 mm, 3 um) column and the followinggradient are used:

Time (min) % Water % MeOH % 2-propanol 0.00 7 93 0 3.00 7 93 0 4.00 0 0100 15.00 0 0 100 15.01 7 93 0 25.00 7 93 0

The flow rate is 0.3 ml/min, and the injection volume is 1.00 ml. Themass spectrometer is operated with the following settings:

Optics Mode: V

Ionization: ESi+

Capillary Voltage: 3000

Sample Cone Voltage: 50

Desolvation T (° C.) 300

Source T (° C.) 120

Nitrogen Gas Flow (L/hr.)

Cone: 50

Desolvation: 650

Mass Range: 100-2000

The peak area for each component (i) to (v) are divided by the sum ofthe peak areas for components (i), (ii), (iii), (iv) and (v) and thequotients are multiplied by 100%. The mole percent of the components canbe calculated from the peak area percents, as determined by the liquidchromatographic-mass spectrometric (LC-MS) method described above andsetting the response factor, which is the mole percent per peak areapercent, for each of the components (i), (ii), (iii), (iv) and (v) equalto 1.

In still another embodiment, the number average molecular weight of theepoxy-containing polysiloxane oligomer composition is determined by agel permeation chromatographic method (GPC). The GPC methods involvesusing a Waters 2690 Chromatograph equipped with Waters 2460 VariableWavelength UV and Waters 2420 ELS detectors and Waters Millenium Systemdata collection. This detector is typically used for concentrationoperating at 45° C. utilizing N₂ as a nebulizing gas. The columns areone 100×4.6 mm guard column and two 300×7.6 mm linear mixed bed columnswith a reported molecular weight range of 100-20,000,000 (polystyrene).All columns are packed with 5 micron particle size,styrene-divinylbenzene beads and have 0.2 micron inlet frits and 0.5micron outlet frits and manufactured by Phenomenex Spherogel Linear(2).The operating conditions are:

Solvent: chloroform.

Flow rate: 1.0 mL/min.

Injection volumes: 10 microliters.

Sample concentrations: 1.0-1.5% by weight.

All samples are filtered through 0.45 micron disposable filters toremove undissolved particulate matter. The calibrations are based uponnarrow molecular weight polystyrene standards that ranged from 264 gramsper mole to 2,800,000 grams per mole. To correct small flow ratechanges, a drop of toluene is added to each sample and the retentiontime measured by UV absorbance. A retention time correction is performedfor each analysis based on the retention times of the toluene.

The epoxy-containing polysiloxane oligomer composition of the inventionhas many applications. Accordingly, in one embodiment, the presentinvention is directed to a composition comprising

(i) a epoxy-containing polysiloxane oligomer composition of theinvention;

(ii) an organic resin containing at least one functional group selectedfrom the group consisting of epoxy, carboxylic acid, carboxylate anion,amino, ureido, urethane, mercapto, hydroxyl, alkoxysilyl and isocyanato;and

(iii) at least one additional component selected from the groupconsisting of a solvent, surfactant, particulate metal, pigment,biocide, filler, thixotrope, catalyst, curing agent, buffering agent andleveling agent.

Specifically, the organic resin (ii) may be an epoxy resin, anisocyanate-terminated polymer, an alkoxysilyl-terminated polyurethane,an alkoxysilyl-terminated polyether, a polyamide, a polyvinyl acetate,polyvinyl alcohol, polycarbonate, polyamines, copolymers of an alkeneand (meth)acrylic, copolymers of (meth)acrylate ester and (meth)acrylicacid, terpolymers of an alkene, (meth)acrylate ester and (meth)acrylicacid, a urea-extended phenolic resin and a phenolic resin. Morespecifically, the organic resin (ii) is an epoxy resin selected from thegroup consisting of diglycidyl ether of bis-phenol A, diglycidyl etherof bis-phenol F, epoxy phenolic novolac resin, glycidyl ether ofbisphenol, glycidyl ether of aliphatic polyol, glycidyl amide, glycidylamine, thioglycidyl resins, glycidyl ester of dicarboxylic acids,tetraglycidyl ether of tetra phenol ethane, epoxy cresol novolac andcombinations thereof. Commercial epoxy resins that are suitable for usein this inventions are listed in: Handbook of Epoxy Resins, Henry Leeand Kris Neville, McGraw-Hill Book Company, New York (1967), Appendix4-2, the entire contents incorporated herein by reference.

The organic resin (ii) can in the form of an emulsion or a dispersion,in which the resin is emulsified with water using surfactants ordispersed in water. The solids content of the emulsion or dispersion maybe from 0.1 to 70 weight percent, more specifically from 5 to 60 weightpercent and even more specifically from 30 to 55 weight percent, basedupon the total weight of the emulsion or dispersion.

The curing agent is not particularly limited and can be dicarboxylicacids, carboxylic acid anhydrides, aziridines, fatty acid polyamides,dicyandiamide, acrylamides, imidazoles, hydrazidines, ethylene imines,thioureas, sulfonamides, acrylamides, guanamines, melamine, urea,polyamines, imidazoline-polyamines, or polyamine-amides. Representativeand non-liming examples include m-phenylenediamine,4,4′methylenediamine, diaminodiphenylsulfone, benzyldimethylamine,benzyldiethylamine, dimethylethanolamine, diethylethanolamine,2-picoline, 4-picoline, 2,6,lutidine and mixtures thereof.

Suitable solvents include water, alcohols, ketones, esters, amides,ether-alcohols, hydrocarbons, and mixtures thereof. Representative andnon-limiting solvent include water, methanol, ethanol, propanol,isopropanol, butanol, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, ethylene glycol monopropyl ether, ethylene glycolmonobutyl ether, ethylene glycol monohexyl ether, ethylene glycolmono-2-ethylhexyl ether, ethylene glycol monophenyl ether, diethyleneglycol monomethyl ether, diethylene glycol monoethyl ether, diethyleneglycol monopropyl ether, diethylene glycol monobutyl ether, butylcarbitol, dipropylene glycol dimethyl ether, butyl glycol, butyldiglycol, ethylene glycol monomethyl ether acetate, ethylene glycolmonobutyl ether acetate, diethylene glycol monoethyl ether acetate,diethylene glycol monobutyl ether acetate, n-propyl acetate, n-butylacetate, isobutyl acetate, methoxypropyl acetate, butyl cellosolveacetate, butylcarbitol acetate, propylene glycol n-butyl acetate,t-butyl acetate, propylene glycol, 2-butoxyethanol, methylethyl ketone,dimethyl ketone, ethyl acetate, ethyl propanoate, dimethylformamide,toluene, xylene, mineral spirits, naphta, and mixtures thereof. Thesolvent is present in the amount ranging from 0.1 to 99 weight percent,more specifically from 5 to 90 weight percent and even more specificallyfrom 15 to 80 weight percent, based upon the total weight of thecomposition to which the solvent is to be added.

The surfactant can be a cationic surfactant, anionic surfactant or anon-ionic surfactant or any combination thereof. The surfactant has ahydrophilic-lipophilic balance (HLB) ranging from 5 to 13. The amount ofsurfactant can be in the range of from 0.1 to 6 weight percent, morespecifically from 1 to 5 weight percent, based upon the total weight ofthe composition to which the solvent is to be added. Representative andnon-limiting examples of surfactants include alkyl-phenol-ethoxylatesurfactant, polyether siloxane based surfactant, quaternary ammoniumhalide surfactant, alkyl phosphate salts of ammonium, alkali or earthalkaline metal ion, organic phosphate esters, diether sulfosuccinates,or mixtures thereof.

The particulate metal can be a corrosion protection filler or a pigment.The particulate metal is any finely divided aluminum, manganese,cadmium, nickel, stainless steel, tin, magnesium, zinc, alloys thereofor ferroalloy, or salts or metal organic inhibitors or metal phosphates.More specifically, the particulate metal is zinc dust, zinc flake,aluminum dust, or aluminum in a powder or paste dispersion form. Theparticulate metal may be a mixture of any of the foregoing, as well asalloys and intermetallic mixtures thereof. Flake may be blended withpulverulent metal powder, but typically with only minor amounts ofpowder. The metallic powders typically have particle size such that allparticles pass 100 mesh and a major amount passes 325 mesh (“mesh” asused herein is U.S. Standard Sieve Series). The powders are generallyspherical as opposed to the leafing characteristics of the flake. Wherethe metal particulate is a combination of zinc with aluminum, thealuminum may be present in very amounts, ranging from 2 to 50 weightpercent of the particulate metal. The particulate metal includes metaloxides, such as cerium oxide, aluminum oxide, iron oxide, silicon oxideand the like. Some particulate metal particles can be dispersed in anaqueous solvent, such as colloidal cerium oxide or colloidal silica. Theparticulate metal content will typically not exceed more than 70 weightpercent of the total weight of the composition, based upon the totalweight of the composition to which the particulate metal is to be added,but is preferably used in amounts of 1.5 to 35 weight percent. Otherparticulate metal also include metal salts, where representative andnon-limiting examples are zinc chromates, zinc potassium chromates, zincphosphates, aluminotriphosphates, aluminum zinc phosphates, molybdates,wolframates, zirconates and vanadates, zinc salts of 5-nitrophtalic acidor iron phoshide.

The thickener is a polymeric compound that contributes to the viscosityof the composition. A thickener may be water-soluble cellulose ether,xanthan gum, urethane associative thickeners, urethane-free nonionicassociate thickeners, which are typically opaque, high-boiling liquids,or modified clays. The thickener, when present, can contribute an amountof between 0.01 and 2 weight percent, based upon the total weight of thecomposition to which the thickener is to be added. Representative andnon-limiting thickeners include ether of hydroxyethylcellulose,methylcellulose, methylethylcellulose, highly beneficiated hectoriteclay, organically modified and activated smectite clay or mixturesthereof. When thickener is used, it is usually the last ingredient addedto the composition.

Fillers may include those for density modification, physical propertyimprovements such as mechanical properties or sound absorption, fireretardancy or other benefits including those that may involve improvedeconomics. For example, calcium carbonate or other fillers can reducethe cost of manufactured composition; aluminum trihydrate or other fireretardant fillers can improve fire retardancy; barium sulfate or otherhigh-density filler can be used for sound absorption; microspheres ofmaterials such as glass or polymers can improve physical properties.Fillers of high aspect ratio that are used to modify mechanicalproperties such as stiffness or flexural modulus include man-made fiberssuch as milled glass fiber or graphite fiber, natural mineral fiberssuch as wollastonite, natural animal fibers such as wool or plant fiberssuch as cotton, man-made plate-like fillers such as shattered glass andnatural mineral plate-like fillers such as mica. When used, filler canbe used at amount ranging from 0.1 to 80 weight percent, and morespecifically from 5 to 50 weight percent, based upon the total weight ofthe composition to which the filler is to be added.

The composition may include surface active agents for reducing foam,aiding in de-aeration, or in modifying a surface, such as increase inmar resistance, reduced coefficient of friction, flatting or levelingeffects, and improved abrasion resistance. The surface-active materialmay include silicone-based materials, such as a polyether siliconecopolymers and silicone oils, and hydrophobized silica particles. Thesesurface-active materials are typically used in the range of from 0.01weight percent to 5 weight percent, based upon the total weight of thecomposition to which the surface-active agent is to be added.Representative and non-limiting surface active materials includeCoatOSil* 100E deformer, CoatOSil* 1211 wetting agent, CoatOSil* 1220surfactant, CoatOSil* 1221 surfactant, CoatOSil* 3500, CoatOSil* 3501,CoatOSil* 3505 or CoatOSil* 3573 agent used to reduce the coefficient offriction. CoatOSil* 3509 agent used to improve mar resistance andCoatOSil* 7001E agent, used to level and flow, all sold commercially byMomentive Performance Materials Inc.

A biocide is a chemical substance or microorganism which can deter,render harmless or exert a controlling effect on any harmful organism bychemical or biological means. A biocide can be a pesticide or anantimicrobial agent. Many biocides are synthetic, but a class of naturalbiocides, derived from bacteria and plants. Biocides are used at amountsranging from 0.01 weight percent to 2 weight percent, based upon thetotal weight of the composition to which the surface-active agent is tobe added. Representative and non-limiting examples of chemical biocidesinclude acrolein, alphachloralose, aluminum phophide, bifenthrin, boricacid, boric oxide, brodifacoum, bromadilone, chlorophacinone,chothianidin, coumatetralyl, dazomet, dichloofluanid, difenacoum,difethialone, disodium octaborate tetrahydrate, and mixtures thereof.Representative and non-limiting examples of microorganism-based biocidesinclude brassica oleracea, brassica oleracea gemmifera, and clostridiumbotulinum bacteria.

The epoxy-containing polysiloxane oligomer compositions of the presentinvention can be used as a component in coatings, sealants, adhesives ormineral filled composites. In use, these coatings, sealants, adhesivesor mineral filled composites can be applied to a desired substrate byconventional techniques. Illustrative of substrates include plastic,metal, wood, concrete, and vitreous surfaces. Accordingly, in oneembodiment, the present invention is directed to a substrate having acomposition applied thereto, wherein the composition contains (i) aepoxy-containing polysiloxane oligomer composition of the invention;(ii) an organic resin containing at least one functional group selectedfrom the group consisting of epoxy, carboxylic acid, carboxylate anion,amino, ureido, urethane, mercapto, hydroxyl, alkoxysilyl and isocyanato:and (iii) at least one additional component selected from the groupconsisting of a solvent, surfactant, particulate metal, pigment,biocide, filler, thixotrope, catalyst, curing agent, and leveling agent.The composition can be cured to provide desired properties to thesubstrate.

Advantageously, epoxy-containing polysiloxane oligomer compositions ofthe present invention are useful as additive for coatings to improve thechemical resistance while maintaining the flexibility of the curedcoating and not contributing VOCs into the environment during use. Thecoatings containing the epoxy-containing polysiloxane oligomercomposition of the present invention may include powder coatings,conversion coatings, passivation coatings, primers, high solids coating,waterborne coatings, solventborne coatings, e-coatings, hardcoats andthe like. These coatings may be used to decorate a surface, to protectfrom abrasion, chemical etching or marring, to inhibit corrosion ofmetal surfaces, to bond different coating together or to the surface, toinhibit fouling of surfaces by biological organisms, or to improve theslip resistance of the surface.

The following examples are intended to illustrate, but in no way limitthe scope of the present invention. All parts and percentages are byweight and all temperatures are in degrees Celsius unless explicitlystated otherwise.

EXAMPLES Example 1 Preparation of Epoxy-Containing Polysiloxane OligomerComposition 1

Two 5-liter round bottom reaction flasks equipped with a mechanicalstirrer, condenser, and temperature probe were charged with silane,water and catalysts. In the first flask,3-glycidoxypropylmethyldiethoxysilane (3262.0 grams, 13.1 moles ofSilquest* A-2287, available from Momentive Performance Materials Inc.)and water containing acetic acid catalyst (1427.6 grams solution, 79.3moles water and 2.4×10⁻⁴ mole acetic acid) were charged. In the secondflask, 3-glycidoxypropylmethyldiethoxysilane (3252.9 grams, 13.1 molesof Silquest* A-2287, available from Momentive Performance MaterialsInc.) and water containing acetic acid catalyst (1414.3 grams, 78.6moles water and 2.4×10⁻⁴ mole acetic acid) were charged. The mixtureswere stirred for a period of 96 hours at ambient temperature to effectthe hydrolysis of the silane. The flasks were then equipped with adistillation head. Water and ethanol were removed from the distillationunit as an azeotrope at an initial temperature of 23-24° C. and pressureof 16.0 kilopascal to 17.3 kilopascal (120-130 mmHg) and slowly raisedin temperature to remove the remaining azeotrope. The temperature wasfurther raised to a final temperature of 60° C. and the pressure loweredto a final pressure ranging from 0.013 kilopascal to 1.2 kilopascal (0.1to 9 mmHg) to remove the water and to condense the silanol. The contentsof the two reaction vessels were then combined into one reaction vessel,and any remaining volatiles were removed at a temperature of 60° C. anda pressure of 0.26 kilopascal (2 mmHg). The reaction vessel was thensparged with nitrogen for 11 hours at 70-80° C. at 13.3 kilopascal (100mmHg). After sparging, boric acid (1.2 grams, available fromSigma-Aldrich) was charged to the reaction vessel to provideepoxy-containing polysiloxane oligomer composition 1. The compositionwas analyzed to have the following properties:

Epoxy Content: 5.32 meq/gram by titration

Oligomer Distribution as determined by the LC-MS method, describedherein:

component (i) 16.3 mole percent;

component (ii) 40.7 mole percent

component (iii) 31.6 mole percent;

component (iv) 11.2 mole percent;

component (v) 0.2 mole percent.

Other components included a hexamer at 2 mole percent, and a heptamer atless than <0.5 mole percent.

Viscosity: 177 centistokes, by bubble viscometer at 20° C.

Ethanoxy or Ethanol: 0 mole percent (not detected) by the 13-C NMRmethod, described herein.

Example 2 Preparation of Epoxy-Containing Polysiloxane OligomerComposition 2

3-Glycidoxypropylmethyldiethoxysilane (248 grams, 1 mole) was chargedinto a 3-necked round bottom flask quipped with a mechanical stirrer.Aqueous boric acid solution (108 grams solution, 6 moles water and 0.054grams boric acid, 8.75×10⁻⁴ mole boric acid) was added to the flask andstirred at room temperature of approximately 25° C. and atmosphericpressure over a period of 16 hours. The reaction flask was then equippedwith a distillation head and a vacuum pump. The mixture was heated to atemperature of 78-80° C. to remove the azeotrope of ethanol and waterand then volatile byproduct water was removed with the application ofvacuum over a period of 3 hours. The epoxy-containing polysiloxaneoligomer composition 2 was cooled to room temperature and stored undernitrogen. The analyses of the product were:

Epoxy Content: 5.49 meq/gram by titration

Oligomer Distribution as determined by the LC-MS method, describedherein:

component (i) 15.3 mole percent;

component (ii) 42.8 mole percent

component (iii) 30.5 mole percent;

component (iv) 11.2 mole percent;

component (v) 0.2 mole percent.

Other components included a hexamer at 2 mole percent, and a heptamer atless than <0.5 mole percent.

Viscosity: 125 centistokes, by bubble viscometer at 20° C.

Ethanoxy or Ethanol content: 0.5 mole percent by the 13-C NMR method,described herein.

Example 3 Preparation of Epoxy-Containing Polysiloxane OligomerComposition 3

3-Glycidoxypropylmethyldiethoxysilane (1464.56 grams, 5.89 moles,available from Momentive Performance Materials Inc.) and aqueous aceticacid solution (655.25 grams solution, 36.4 moles water, 1.0×10⁻⁴ moleacetic acid) were charged into a round bottom flask equipped with amechanical stirrer, condenser, and temperature probe. The mixture wasstirred for a period of 24 hours at ambient temperature to hydrolyze thesilane. After equipping the flask with a distillation head, the mixturewas heated to a temperature of 23° C. at 12.1 kilopascal (91 mmHg)pressure, which was slowly increased to a temperature of 30° C. at apressure of 0.7 kilopascal (5 mmHg) to remove the ethanol and water. Thereaction vessel was then sparged with nitrogen for 4.5 hours at atemperature of 90° C. and a pressure of 10.8 kilopascal (81 mmHg).2-Methyl-1,3-propanediol (20.46 grams) was mixed with theepoxy-containing polysiloxane oligomer composition (173.57 grams).

Oligomer Distribution as determined by the LC-MS method, describedherein:

component (i) 24.0 mole percent;

component (ii) 46.2 mole percent

component (iii) 18.6 mole percent;

component (iv) 3.7 mole percent;

component (v) 7.5 mole percent.

Other components included a hexamer at 0.4 mole percent.

Comparative Example A Preparation of Comparative Epoxy-Functional SilaneOligomer Composition A

3-Glycidoxypropylmethyldiethoxysilane (36.04 grams, 0.145 moles), water(3.92 grams, 0.22 moles), and Purolite CT-275 Dry Ion Exchange Resinwere charged into a round bottom flask equipped with a mechanicalstirrer, condenser, and temperature probe. The reaction vessel washeated to 74° C. for 3 hours, and subsequently stripped under vacuum ata temperature of 75° C. and 0.11 kilopascal (0.85 mmHg) to providecomparative epoxy-functional silane hydrolyzate composition A. Thecomposition was analyzed using a gas chromatographic method using anAgilent 6850 Series GC system, HP 5 capillary column, helium gascarrier, thermal conductivity detector and a temperature profile of 80°C. for 2 minutes and then a ramp up of 10° C. minute until a temperatureof 250° C. is reached, followed by a 10 minute hold period. Thecomposition contained 13.3 weight percent3-glycidoxypropylmethyldiethoxysilane.

The epoxy-functional silane hydrolyzate composition A contained 13.3weight percent of 3-glycidoxypropylmethyldiethoxysilane because only1.52 moles of water were added per mole of silane in step (a). Thecomposition A contained residual ethoxysilyl groups which, upon use,generated ethanol, a volatile organic compound that contributes toemissions into the environment. The epoxy-containing polysiloxaneoligomer compositions of the present invention do not containsignificant amounts of ethoxysilyl groups and therefore do notcontribute to volatile organic compound emission during use.

Example 4 Stability Tests

The oligomer distribution of the products from Example 1, Example 2 andExample 3 were monitored over time. FIG. 1 is a graph of the weightedpeak area average number of silicon atoms per sum of peak area of allthe components of the composition, as determined using the liquidchromatography-mass spectrometry method over time. It illustrates theeffect of using a stabilizing agent (d) to improve the stability of theepoxy-containing polysiloxane oligomer composition.

As shown in FIG. 1, the product from Example 1 gained 0.0063 Si unitsper day (0.19 Si units per month). The product from Example 2 gained0.0148 Si units per day (0.444 Si units per month). The product fromExample 3 gained 0.0017 Si units per day (0.0521 per month). Theaddition of the boric acid in step (d) produced a relatively more stableepoxy-containing polysiloxane oligomer composition than when boric acidwas added in step (a). The 2-methyl-1,3-propanediol was also aneffective stabilizing agent when used at 11.8 weight percent.

Example 5 Coating Formulations Containing the Epoxy-ContainingPolysiloxane Oligomer Composition of Example 1

Part A: Preparation of Coating Formulation Containing theEpoxy-Containing Polysiloxane Oligomer of Example 1.

A coating formulation comprising the epoxy-containing polysiloxaneoligomer from Example 1, which has a releasable ethoxy/ethanol contentof 0 mole percent was prepared. The epoxy-containing polysiloxaneoligomer from Example 1 (22.72 grams) was added to a 250 mL wide mouthglass jar under agitation. De-ionized water (38.91 grams) was addedfollowed by butyl cellosolve (22.99 grams). Finally, trimethylolpropanetriacrylate (1.41 grams of SR 351, available through Sartomer) was addedto the mixture. The mixture was vigorously agitated by hand forapproximately one minute to form Part A.

Part B: Preparation of Amine Catalyst Blend

Into a 250 mL wide mouth glass jar, a 53% solids, non-ionic aqueousdispersion of a modified polyamine adduct curing agent with an aminevalue of 235 to 265 milligram/gram (155.16 grams of EpiKure 6870-W-53,available from Momentive Specialty Chemicals Inc.) was added. De-ionizedwater (9.00 grams, 0.5 mole) was added with stirring and thentris(dimethyl amino-methyl)phenol (3253, 4.50 grams of EpiKure,available from Momentive Specialty Chemicals Inc.) was added to theglass jar. The blend of materials was vigorously agitated by hand forapproximately one minute. The material was then stored for use as theamine curative blend for Example 5 and Comparative Examples B and C.

The amine curative Part B (62.51 grams) was added to Part A (86.03grams). The mixture was vigorously agitated for one minute prior tospray application.

Comparative Example B Coating Formulation Containing CoatOSil* MP200Epoxy Resin

A coating formulation containing a 3-glycidoxylpropyl polysilsesquioxane(CoatOSil* MP200 which has a releasable methanol, a hazardous airpollutant (HAP) content of ˜20 weight percent and VOC release of ˜200g/L, available from Momentive Performance Materials Inc.) was prepared.CoatOSil* MP200 (24.33 grams) was added to the jar with agitation.De-ionized water (38.70 grams) was added followed by butyl cellosolve(23.10 grams). Finally, trimethylolpropane triacrylate (1.41 grams of SR351, available from Sartomer) was added to the mixture, to form Part A.The amine curative prepared in Example 5 (59.54 grams of Part B) wasadded to Part A (86.13 grams). The mixture was vigorously agitated forone minute prior to spray application.

Comparative Example C Coating Formulation Absent of Epoxy-ContainingPolysiloxane Oligomer of Present Invention

A coating formulation was prepared by adding de-ionized water (38.90grams), butyl cellosolve (22.98 grams), trimethylolpropane triacrylate(1.41 grams of SR351, available through Sartomer) and finally, a 53weight percent solids, non-ionic aqueous dispersion of a modified EPON™Resin 1001 type solid Bis A epoxy (68.40 grams of Epirez 6520-WH-53,available from Momentive Specialty Chemicals Inc.) to a 250 mL glassjar. The mixture was then vigorously agitated by hand for approximatelyone minute to give Part A. To this mixture, the amine curative preparedabove in Example 5 (38.28 grams of Part B) was added to Part A (131.69grams) and vigorously agitated for one minute prior to sprayapplication.

Example 6 and Comparative Examples D and E Testing of the CoatingFormulations from Example 5 and Comparative Examples B and C

The substrate that was used to test the coating compositions was ColdRoll Steel APR10184 substrate available from ACT Test Panels.

The solution to clean the Cold Roll Steel consisted of 0.06 weightpercent Triton X-100, 0.52 weight percent anhydrous sodium metasilicate,0.49 weight percent anhydrous sodium carbonate, 0.35 weight percentsodium phosphate, anhydrous dibasic, all available from Aldrich, and98.57 weight percent de-ionized water.

The Cold Roll Steel panels were cleaned. The cleaning solution washeated to a temperature of between 65° C. to 70° C. The Cold Roll Steelpanels were immersed into the stirred, heated cleaning solution for 2 to3 minutes to remove any oil contaminants. The panels were removed fromthe solution and immediately rinsed with de-ionized water. KimwipeKimtech Delicate Task Wipers, available from Kimberly Clark, were thenused to wipe the panels dry. The panels were then lightly sprayed withwater to determine the water break of the cleaned panels, in accordingto ASTM F-22, “Standard Method of Test for Hydrophobic Surface Films bythe Water Break Test. If the panels showed water beading, then thecleaning process was repeated. If the water formed a continuous sheen,then the panels were then dried with a Kimwipe wiper and stored for use.

The coating formulations from Example 5 and Comparative Examples B and Cwere then spray applied over the bare Cold Roll Steel panels. Sprayapplication was conducted with a StartingLine HVLP gravity fed siphonspray hand spraygun, available through DeVilbiss. The coatings weresprayed at a wall pressure of 241.3 kilopascal (35 lb/in²). The sprayapplication technique was a side-to-side sweep of the spray onto thepanel at a rate of approximately 2,540 centimeter/minute (1,000inches/minute), indexing up and down the panel approximately 5.0centimeters (2 inches) per sweep until approximately 25.4 microns (1.0mil) of coating thickness was applied on the panel.

The panels were then cured under room temperature conditions for 24hours, and then tested for scrub resistance using methyl ethyl ketone(MEK) Double Rubs according to AATCC 8 using Crockmeter device and 4layers of cheesecloth, for gloss according to ASTM D523, for PencilHardness according to ASTM D3363, and for Gardner Direct & ReverseImpact Strength according to ASTM D2794 using a 4-pound weight. Testresults were measured at 1, 3, and 10 days unless otherwise specified.

The test Results are shown in Tables 1-3 and FIGS. 2 and 3.

TABLE 1 MEK Double Rubs results are presented. The MEK double rubs arereported as the number of double rubs until the metal is exposed oruntil 999+ scrubs were completed. Coating prepared Day Day Day DayExample in Example 1 3 10 40 6 5 999+ 999+ 999+ — D B 999+ 999+ 999+ — EC 21 — — ~800

TABLE 2 Results from Pencil Hardness testing of coating compositionsCoating from Example Example Day 1 Day 3 Day 10 Day 40 Example 6 Example5 — 4H 5H — Comparative Comparative — 4H-5H 4H-5H — Example D Example BComparative Comparative — — — 3H Example E Example C

TABLE 3 Results from impart resistance testing of coating compositions.Coating from Day Day Day Day Example Example 1 3 10 40 DIRECT IMPACTExample 6 Example 5 160 120 80-100 — Comparative Comparative 140  60  40— Example D Example B Comparative Comparative — — — 160 Example EExample C REVERSE IMPACT Example 6 Example 5 160 160 160 — ComparativeComparative 140  60 <20 — Example D Example B Comparative Comparative —— — 160 Example E Example C

The results of the testing indicate that the coating composition ofExample 5 had MEK double rubs in excess of 999, indicating chemicalresistance, and reverse impact of 160, indicating flexibility. Thecoating of Comparative Example B had MEK double rubs in excess of 999,but the reverse impact was less than 20 after 10 days, indicating poorerflexibility than the coating of Example 5. Likewise, the coating ofComparative Example C had MEK rubs of only 21 after 1 day, which slowlyincreased to 800 double rubs after 40 days, indicating poorer chemicalresistance than the coating of Example 5, even though its flexibility,as indicated by the reverse impact, was comparable. Only the coatingcomposition containing the epoxy-containing polysiloxane oligomercomposition of the present invention had good chemical resistancewithout sacrificing flexibility.

Comparative Example F Coating Formulations Containing3-Glycidoxypropylmethyldiethoxysilane

A two-part coating formula was prepared using3-glycioxypropylmethyldiethoxysilane, the precursor silane used to makethe epoxy-containing polysiloxane oligomer composition.

Part A: Preparation of Coating Formulation Containing the3-Glycidoxypropylmethyldiethoxysilane

A coating formulation containing 3-glycidoxypropylmethyldiethoxysilanewas prepared. A medium viscosity hydrogenatedepoxy-4,4′-isopropylidenediphenol resin (28.5 grams of Eponex 1510resin, available from Momentive Specialty Chemicals Inc.), micronizedrutile titanium dioxide (25 grams of Bayertitan R-KB-4, available fromBayer AG), a methoxy functional methylphenyl polysiloxane (14.6 grams ofTSR-165, available from Momentive Performance Materials Inc.) and3-glycidoxypropylmethyldiethoxysilane (9.5 grams of Silquest* A-2287,available from Momentive Performance Materials Inc.) was added to a 250mL wide mouth glass jar under agitation. The mixture was vigorouslyagitated by hand for approximately one minute to form Part A.

Part B: Preparation of Amine Curative Mixture

Into a 250 mL wide mouth glass jar were charged a medium viscosityreactive polyamide curing agent, based on dimerized fatty acid andpoly-amines with an amine content of 330 to 360 milligram/gram (3125,9.2 grams of Epikure curing agent, available from Momentive SpecialtyChemicals Inc.), 3-aminopropyltriethoxysilane (11.2 grams of Silquest*A-1100 silane, available from Momentive Performance Materials Inc.) anddibutyl tin dilaurate (2 grams of Fomrez tin catalyst SUL-4, availablefrom Momentive Performance Materials Inc.). The blend of materials wasvigorously agitated by hand for approximately one minute.

Part A and Part B were mixed and vigorously agitated for one minuteprior to spray application.

Example 7 Coating Formulation Containing Epoxy-Containing PolysiloxaneOligomer Prepared in Example 2 Part A: Preparation of CoatingFormulation Containing the Epoxy-Containing Polysiloxane OligomerPrepared in Example 2

A coating formulation containing epoxy-containing polysiloxane oligomerof Example 2 was prepared. A medium viscosity hydrogenatedepoxy-4,4′-isopropylidenediphenol resin (27.8 grams of Eponex 1510resin, available from Momentive Specialty Chemicals Inc.), micronizedrutile titanium dioxide (25 grams of Bayertitan R-KB-4, available fromBayer AG), a methoxy functional methylphenyl polysiloxane (14.6 grams ofTSR-165, available from Momentive Performance Materials Inc.) andepoxy-containing polysiloxane oligomer composition prepared in Example 2(9.3 grams) was added to a 250 mL wide mouth glass jar under agitation.The mixture was vigorously agitated by hand for approximately one minuteto form Part A.

Part B: Preparation of Amine Curative Mixture

Into a 250 mL wide mouth glass jar were charged a medium viscosityreactive polyamide curing agent, based on dimerized fatty acid andpoly-amines with an amine content of 330 to 360 milligram/gram (3125,9.6 grams of Epikure curing agent, available from Momentive SpecialtyChemicals Inc.), 3-aminopropyltriethoxysilane (11.7 grams of Silquest*A-1100 silane, available from Momentive Performance Materials Inc.) anddibutyltin dilaurate (2 grams of Fomrez tin catalyst SUL-4, availablefrom Momentive Performance Materials Inc.). The blend of materials wasvigorously agitated by hand for approximately one minute.

Part A and Part B were mixed and vigorously agitated for one minuteprior to spray application.

Example 8 and Comparative Example G Testing of the Coating Formulationsfrom Example 7 and Comparative Example F

The substrate that was used to test the coating compositions was ColdRoll Steel APR10184 substrate available from ACT Test Panels.

The solution to clean the Cold Roll Steel consisted of 0.06 weightpercent Triton X-100, 0.52 weight percent anhydrous sodium metasilicate,0.49 weight percent anhydrous sodium carbonate, 0.35 weight percentsodium phosphate, anhydrous dibasic, all available from Aldrich, and98.57 weight percent de-ionized water.

The Cold Roll Steel panels were cleaned. The cleaning solution washeated to a temperature of between 65° C. to 70° C. The Cold Roll Steelpanels were immersed into the stirred, heated cleaning for 2 to 3minutes to remove any oil contaminants. The panels were removed from thesolution and immediately rinsed with de-ionized water. Kimwipe KimtechDelicate Task Wipers, available from Kimberly Clark, were then used towipe the panels dry. The panels were then lightly sprayed with water todetermine the water break of the cleaned panels. If the panels showedwater beading, then the cleaning process was repeated. If the waterformed a continuous sheen, then the panels were then dried with aKimwipe wiper and stored for use.

The coating formulations from Example 7 and Comparative Examples F werethen spray applied over the bare Cold Roll Steel panels to form testpanels for Example 8 and Comparative Example G, respectively. Sprayapplication was conducted with a StartingLine HVLP gravity fed siphonspray hand spraygun, available through DeVilbiss. The coatings weresprayed at a wall pressure of 241.3 kilopascal (35 lb/in²). The sprayapplication technique was a side-to-side sweep of the spray onto thepanel at a rate of approximately 2,540 centimeter/minute (1,000inches/minute), indexing up and down the panel approximately 5.0centimeters (2 inches) per sweep until approximately 25.4 microns (1.0mil) of coating thickness was applied on the panel.

The panels were then cured under room temperature conditions for 24hours, and then tested for scrub resistance using methyl ethyl ketone(MEK) Double Rubs according to AATCC 8 using Crockmeter device and 4layers of cheesecloth, and for gloss according to ASTM D523. The glossretention was measure before and after 200 MEK double rubs. The resultsof the testing are reported in Table 4.

TABLE 4 Gloss retentions for coating formulations the test results forGloss @ 60° after Coating from Initial gloss 200 double-hubs GlossExample Example @ 60° with MEK retention Example G Example F 82° 65° 79%Example 8 Example 7 89° 85° 96%

The coating composition containing epoxy-containing polysiloxaneoligomer composition from Example 2 had initial gloss and glossretention better than the similar coating composition containing themonomeric silane, 3-glycidoxypropylmethyldiethoxysilane. The glossretention of 96% for the coating of Example 7 indicates better chemicalresistance than observed for Comparative Example G, which had only 79%gloss retention.

The foregoing description of the specific embodiments will so fullyreveal the general nature of the invention that others can, by applyingknowledge within the skill of the art, readily modify and/or adapt forvarious applications such specific embodiments, without undueexperimentation, without departing from the general concept of thepresent invention. Therefore, such adaptations and modifications areintended to be within the meaning and range of equivalents of thedisclosed embodiments, based on the teaching and guidance presentedherein, and it is intended that the invention embrace all suchadaptations and modifications that fall within the spirit and broadscope of the appended claims. It is to be further understood that thephraseology or terminology herein is for the purpose of description andnot of limitation, such that the terminology or phraseology of thepresent specification is to be interpreted by the skilled artisan inlight of the teachings and guidance.

What is claimed is:
 1. A process for making an epoxy-containingpolysiloxane oligomer composition wherein the composition comprises, (i)from 5 to 65 mole percent of a polysiloxane of the Formula (I):

(ii) from 10 to 55 mole percent of a polysiloxane of the Formula (II):

(iii) from 5 to 45 mole percent of a polysiloxane of the Formula (III):

(iv) from 1 to 20 mole percent of a polysiloxane of the Formula (IV):

and (v) from 0.1 to 20 mole percent of a polysiloxane of the Formula(V):

wherein each occurrence of R¹ is —CH₂CH₂CH₂— and the mole percent ofcomponents (i), (ii), (iii), (iv) and (v) are based upon the sum of themolar amounts of components (i), (ii), (iii), (iv) and (v), and whereinthe process comprises: (a) hydrolyzing a silane of the general Formula(VI)

wherein: R¹ is —CH₂CH₂CH₂—; R² is a monovalent alkyl group of from 1 to3 carbon atoms; and R³ is a monovalent alkyl group of from 1 to 3 carbonatoms; in the presence of 2 to 15 moles of water per mole of the silaneand, optionally, a hydrolysis catalyst, at a temperature of from 10° to100° C. to provide an intermediate containing a silanol and an alcohol;(b) removing the alcohol by distillation; (c) removing water to condensethe silanol to the desired polysiloxane oligomer composition comprisingfrom 5 to 65 mole percent of the polysiloxane of the Formula (I), from10 to 55 mole percent of the polysiloxane of the Formula (II), from 5 to45 mole percent of the polysiloxane of the Formula (III), from 1 to 20mole percent of the polysiloxane of the Formula (IV), and from 0.1 to 20mole percent of the polysiloxane of the Formula (V), wherein theFormulae (I), (II), (III), (IV) and (V) are as defined above, whereinthe mole percents of components (i), (ii), (iii), (iv) and (v) are basedupon the sum of the molar amounts of components (i), (ii), (iii), (iv)and (v); and optionally (d) adding a stabilizing agent, thereby makingthe epoxy-containing polysiloxane oligomer composition.
 2. The processof claim 1, wherein the step (b) is carried out under a pressure of from0.1 kilopascal to 200 kilopascal.
 3. The process of claim 1, wherein thestep (c) is carried out under a pressure of from 0.1 kilopascal to 200kilopascal.
 4. The process of claim 1, wherein the stabilizing agent hasthe Formula (VII):R⁴(OR⁵)_(p)  (VII) wherein: R⁴ is a boron atom, a HP(═O)(—)₂ group, aP(═O)(—)₃ group, a R⁶C(═O)(—) group, a polyvalent hydrocarbon groupcontaining from 3 to 20 carbon atoms or a polyvalent heterocarbon groupcontaining from 3 to 20 carbon atoms; each R⁵ is independently ahydrogen, a R⁶C(═O)(—) group, or a hydrocarbon containing from 1 to 6carbon atoms; each R⁶ is independently a monovalent hydrocarboncontaining from 1 to 5 carbon atoms; and p is an integer of from 1 to 6.5. The process of claim 4, wherein the stabilizing agent is selectedfrom the group consisting of boric acid, phosphoric acid, phosphorusacid, acetic acid, acetic acid anhydride, glycerol,2-methyl-1,3-propanediol, 1-methoxy-2,3-propanediol, 1,2-hexanediol, and2,3-dimethyl-2,3-butanediol.
 6. The process of claim 1, furthercomprising carrying out the reaction of step (a) in the presence of acatalyst.
 7. The process of claim 6, wherein the catalyst is selectedfrom the group consisting of metal salts, carboxylic acids, mineralacids or metal chelates.
 8. A composition comprising: (A) anepoxy-containing polysiloxane oligomer composition which comprises: (i)from 5 to 65 mole percent of a polysiloxane of the Formula (I):

(ii) from 10 to 55 mole percent of a polysiloxane of the Formula (II):

(iii) from 5 to 45 mole percent of a polysiloxane of the Formula (III):

(iv) from 1 to 20 mole percent of a polysiloxane of the Formula (IV):

and (v) from 0.1 to 20 mole percent of a polysiloxane of the Formula(V):

wherein each occurrence of R¹ is —CH₂CH₂CH₂— and the mole percent ofcomponents (i), (ii), (iii), (iv) and (v) are based upon the sum of themolar amounts of components (i), (ii), (iii), (iv) and (v); (B) anorganic resin containing at least one functional group selected from thegroup consisting of epoxy, carboxylic acid, carboxylate anion, amino,ureido, urethane, mercapto, hydroxyl, alkoxysilyl and isocyanato; and,(C) at least one additional component selected from the group consistingof a solvent, surfactant, particulate metal, pigment, biocide, filler,thixotrope, catalyst, curing agent, and leveling agent.
 9. Thecomposition of claim 8, wherein the organic resin (B) is an epoxy resin,an isocyanate-terminated polymer, an alkoxysilyl-terminatedpolyurethane, an alkoxysilyl-terminated polyether, a polyamide, apolyvinyl acetate, a polyvinyl alcohol, a polycarbonate, a polyamine, acopolymer of an alkene and (meth)acrylic, a copolymer of (meth)acrylateester and (meth)acrylic acid, a terpolymer of an alkene, (meth)acrylateester and (meth)acrylic acid, a urea-extended phenolic resin, a phenolicresin, or combination thereof.
 10. The composition of claim 8, whereinthe organic resin (B) is an emulsion or a dispersion.
 11. Thecomposition of claim 8, wherein the organic resin (B) is an epoxy resinselected from the group consisting of diglycidyl ether of bis-phenol A,diglycidyl ether of bis-phenol F, epoxy phenolic novolac resin, glycidylether of bisphenol, glycidyl ether of aliphatic polyol, glycidyl amide,glycidyl amine, thioglycidyl resins, glycidyl ester of dicarboxylicacids, tetraglycidyl ether of tetra phenol ethane, epoxy cresol novolac,and combinations thereof.
 12. The composition of claim 8, wherein thecuring agent is selected from group consisting of dicarboxylic acids,carboxylic acid anhydrides, aziridines, fatty acid polyamides,dicyandiamide, acrylamides, imidazoles, hydrazidines, ethylene imines,thioureas, sulfonamides, acrylamides, guanamines, melamine, urea,polyamines, imidazoline-polyamines, and polyamine-amides.
 13. Thecomposition of claim 8, wherein the solvent is selected from the groupconsisting of water, alcohols, ketones, esters, amides, ether-alcohols,and mixtures thereof.
 14. The composition of claim 8, wherein thecomposition is a coating, a sealant, an adhesive or a composite.
 15. Thecomposition of claim 14, wherein the coating is selected from the groupconsisting of powder coatings, conversion coatings, passivationcoatings, primers, high solids coatings, waterborne coatings,solventborne coatings, e-coatings and hardcoats.
 16. The composition ofclaim 15, wherein the coating is selected from the group consisting ofconversion coatings and passivation coatings.
 17. A substrate having thecomposition of claim 8 applied thereto.
 18. The substrate of claim 17wherein the composition is cured.